Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C255/53—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and hydroxy groups bound to the carbon skeleton

Definitions

• This invention relates to the preparation of pesticidal cyclopropane carboxylic acid ester derivatives.
• Cyclopropane carboxylic acid ester derivatives of general formula ##STR2## wherein R 1 and R 2 are independently selected from chlorine, bromine and methyl, are known compounds having pesticidal activity, see for example U.K. Patent Specification No. 1,413,491 or U.S. Pat. No. 4,024,163. These derivatives are members of a class of pesticidal compounds commonly referred to in the art as "pyrethroid insecticides".
• Compounds of formula I contain two centres of asymmetry in the cyclopropane ring of the acid moiety and a third centre of asymmetry in the alcohol moiety, leading to the existence of eight possible isomers.
• superior pesticidal activity resides among the compounds having cis-configuration about the cyclopropane ring, as disclosed by Itaya et al in "Synthetic Pyrethroids", ACS Symposium Series 42, Pages 45 to 54, and the isomer which has the greatest pesticidal activity is generally that isomer which is conveniently designated the 1R cis S-isomer, 1R cis-designating configuration in the acid moiety and S-designating configuration in the alcohol moiety, as described in Elliott et al in Nature, Vol. 248, Pages 710 and 711 (1974).
• a process for preparing a mixture of cis-isomers of a compound of formula ##STR3## wherein R 1 and R 2 are independently selected from chlorine, bromine and methyl, consisting predominantly of the 1R cis-S- and 1S cis R-isomers which process comprises dissolving a mixture of 1S cis S- and 1R cis R-isomers of the compound of formula I, alone or in the presence of 1R cis S- and 1S cis R-isomers, in an organic amine base containing from 5 to 7 atoms and being a secondary amine containing two branched alkyl groups or a tertiary amine, crystallising out from a resulting solution of cis-isomers of formula I in the organic amine base of 1:1 mixture of the 1R cis S- and 1S cis R-isomers, and evaporating off the organic amine base.
• R 1 and R 2 are both chlorine or bromine atoms, and they are preferably both chlorine atoms.
• the organic base causes racemisation to take place at the ⁇ -carbon atom of the alcohol moiety of the compound of formula I, so that the mixture of cis-isomers of formula I in solution in the organic base tends to become a racemic solution of all four cis-isomers, i.e. a solution containing equal quantities of 1R cis S-, 1S cis S-, 1R cis R- and 1S cis R-isomers, assuming that the initial mixture was optically inactive.
• the organic amine bases which are suitable for use in the process of the invention have the further property of being solvents in which the 1R cis S-/1S cis R-enantiomer pair of the isomers of formula I is substantially less soluble than the 1S cis S-/1R cis R-enantiomer pair.
• the precise isomer constitution of the product of the process will be dependent on the balance between the rate of crystallisation, the rate of racemisation and the rate of evaporation. All of these rates will vary according to temperature. The rate of evaporation will also vary according to pressure.
• the starting material is partly or wholly crystalline, in order to ensure complete dissolution of the 1S cis S- and 1R cis R-isomers of the compound of formula I, it is preferred to dissolve the mixture of isomers of formula I in the organic amine base at elevated temperature, e.g. a temperature in the range 50° to 80° C., conveniently 60° to 70° C. If desired the resulting solution may be filtered in order to ensure the absence of any solid particles in the solution prior to crystallisation.
• the starting material is in the form of an oil, e.g., in the case of a freshly prepared racemic mixture of cis-isomers, the mixture of isomers of formula I is advantageously dissolved in the organic amine base at ambient temperature.
• Crystallisation may advantageously be effected at ambient temperature or below, and, where elevated temperatures have been employed in order to bring the mixture of cis-isomers into solution in the organic amine base, crystallisation is preferably effected by cooling the solution to ambient temperature or below.
• crystallisation is initiated by seeding with a few crystals of 1:1 mixture of the 1R cis S- and 1S cis R-isomers of the compound of formula I.
• organic amine base which is evaporated off may readily be condensed and collected in known manner for re-use.
• the product of the process of the invention will always contain more than 50% by weight of the 1R cis S- and 1S cis R-isomers, and provided that the rate of evaporation of the organic amine base is kept sufficiently slow, and that the initial mixture of cis-isomers was optically inactive the product may consist substantially entirely of a 1:1 mixture of 1R cis S- and 1S cis R-isomers of the compound of formula I.
• the preferred organic amine bases contain six carbon atoms. Triethylamine and diisopropylamine have been found to be very effective organic amine bases. Of these, triethylamine is particularly preferred.
• the amount of water in the organic amine base should be less than 2% by weight of the base, advantageously less than 1%, more advantageously less than 0.5%, and the dissolution, crystallisation and evaporation are preferably carried out under substantially anhydrous conditions.
• the product of the process of the invention contains a high proportion of the most pesticidally-active isomer of the relevant compound of formula I.
• the invention also extends therefore to a mixture of cis-isomers of a compound of formula I consisting predominantly of the 1R cis S- and 1S cis R-isomers whenever prepared by the process of the invention, to a pesticidal composition comprising the said mixture in association with a suitable carrier therefor, and to a method of combating pests at a locus which comprises applying to the locus an effective amount of the said mixture or a composition containing the said mixture.
• suitable pesticidal compositions is described in the aforementioned U.K. Patent Specification No. 1,413,491.
• Examples 1 and 2 relates to an embodiment of the process of the invention and Examples 3 and 4 relate to tests indicative of the suitability of organic amine systems for use in the process of the invention.
• Examples 1 to 3 were carried out under substantially anhydrous conditions, the water content of the triethylamine being 0.1% w/w.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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Citations (7)

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• 1981
  • 1981-03-04 CA CA000372319A patent/CA1150730A/fr not_active Expired
  • 1981-04-10 US US06/252,892 patent/US4436667A/en not_active Expired - Lifetime
  • 1981-04-15 BE BE1/10202A patent/BE888431A/nl not_active IP Right Cessation
  • 1981-04-20 BR BR8102378A patent/BR8102378A/pt not_active IP Right Cessation
  • 1981-04-21 JP JP5929381A patent/JPS56166164A/ja active Granted
  • 1981-04-21 DE DE19813115857 patent/DE3115857A1/de active Granted
  • 1981-04-21 AU AU69676/81A patent/AU536529B2/en not_active Expired
  • 1981-04-21 AT AT0179681A patent/AT372676B/de active
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  • 1981-04-21 CH CH259981A patent/CH646420A5/de not_active IP Right Cessation
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  • 1981-04-21 SU SU813273758A patent/SU1238729A3/ru active
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  • 1981-04-21 IT IT21309/81A patent/IT1137381B/it active
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  • 1981-04-21 DK DK178181A patent/DK157613C/da not_active IP Right Cessation
  • 1981-04-21 NL NL8101938A patent/NL8101938A/nl active Search and Examination
  • 1981-04-21 FR FR8107911A patent/FR2481275A1/fr active Granted
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  • 1981-04-21 SE SE8102526A patent/SE453080B/sv not_active IP Right Cessation
  • 1981-04-22 IE IE898/81A patent/IE51196B1/en not_active IP Right Cessation
  • 1981-04-22 NZ NZ196880A patent/NZ196880A/xx unknown

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